(1Z)-1-[(2E)-3-(4-Bromo­phen­yl)-1-(4-fluoro­phen­yl)prop-2-en-1-yl­idene]-2-(2,4-dinitro­phen­yl)hydrazine

Rajni Kant; Vivek K Gupta; Kamini Kapoor; M Sapnakumari; B K Sarojini; B Narayana

doi:10.1107/S1600536812027328

. 2012 Jun 23;68(Pt 7):o2193. doi: 10.1107/S1600536812027328

(1Z)-1-[(2E)-3-(4-Bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-ylidene]-2-(2,4-dinitrophenyl)hydrazine

Rajni Kant ^a,^*, Vivek K Gupta ^a, Kamini Kapoor ^a, M Sapnakumari ^b, B K Sarojini ^c, B Narayana ^b

PMCID: PMC3393993 PMID: 22798858

Abstract

In the title molecule, C₂₁H₁₄BrFN₄O₄, the mean planes of the two nitro groups form dihedral angles of 3.1 (2) and 7.1 (5)° with the benzene ring to which they are attached. The dinitro-substituted ring forms dihedral angles of 8.6 (2) and 71.9 (2)° with the bromo- and fluoro-substituted benzene rings, respectively. The dihedral angle between the bromo- and fluoro-substituted benzene rings is 80.6 (2)°. There is an intramolecular N—H⋯O hydrogen bond. In the crystal, pairs of weak C—H⋯O hydrogen bonds form inversion dimers. In addition, π–π stacking interactions between the bromo- and dinitro-substituted rings [centroid–centroid separation = 3.768 (2) Å] are observed.

Related literature

For applications of hydrazone derivatives, see: Rollas et al. (2007 ▶); Singh et al. (1982 ▶). For the synthesis, see: Jasinski et al. (2010 ▶). For a related structure, see: Yin et al. (2009 ▶).

Experimental

Crystal data

C₂₁H₁₄BrFN₄O₄
M _r = 485.27
Monoclinic,
a = 15.0738 (12) Å
b = 10.6511 (5) Å
c = 14.3353 (8) Å
β = 116.010 (9)°
V = 2068.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 2.03 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.889, T _max = 1.000
15619 measured reflections
4058 independent reflections
2232 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.141
S = 1.01
4058 reflections
280 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.40 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812027328/lh5491sup1.cif

e-68-o2193-sup1.cif^{(26.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812027328/lh5491Isup2.hkl

e-68-o2193-Isup2.hkl^{(194.9KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812027328/lh5491Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H21⋯O1	0.86	1.95	2.584 (4)	130
C11—H11⋯O4ⁱ	0.93	2.45	3.316 (7)	154

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Symmetry code: (i) Inline graphic .

Acknowledgments

RK acknowledges the Department of Science & Technology for access to single-crystal X-ray diffractometer sanctioned as a National Facility under project No. SR/S2/CMP-47/2003. BN thanks the UGC, New Delhi, Government of India, for the purchase of chemicals through the SAP–DRS–Phase 1 programme. MS thanks the DST, New Delhi, for providing financial help for this research work through the INSPIRE Research Fellowship scheme.

supplementary crystallographic information

Comment

Hydrazone derivatives are important biologically active compounds which have received attention from the synthetic community (Rollas et al., 2007). Hydrazone derivatives are also used as analytical reagents (Singh et al., 1982). The crystal structure of 1-(but-2-enylidene)-2-(2-nitrophenyl)hydrazine has been reported (Yin et al., 2009). In order to prepare a pyrazoline derivative, (2E)-3-(4-bromophenyl) -1-(4-fluorophenyl)prop-2-en-1-one was reacted with 2,4-dinitrophenyl hydrazine as for the method of Jasinski et al. (2010). But, instead of a pyrazoline derivative a 2,4-dintrophenylhydrazone compound (I) was obtained and its crystal structure is reported herein.

In (I) (Fig. 1), all bond lengths and angles are normal and correspond to those which are related in a reported structure (Yin et al., 2009). The two nitro groups form dihedral angles of 3.1 (2) and 7.1 (5)° with the C16-C21 ring. The dinitro substituted ring (C16-C21) forms dihedral angles of 8.6 (2)° and 71.9 (2) ° with bromo (C1-C6) and fluoro (C10-C15) substituted benzene rings, respectively. The dihedral angle between the bromo and fluoro substituted benzene rings is 80.6 (2)°. There is an intramolecular N—H···O hydrogen bond and in the crystal, pairs of weak C—H···O hydrogen bonds form inversion dimers (Table 1, Fig. 2). In addition, π–π stacking interactions between the bromophenyl ring and dinitro phenyl ring are observed [centroid separation = 3.768 (2) Å, interplanar spacing =3.410 Å, centroid shift = 1.60 Å, Symmetry = x, 1 + y, z].

Experimental

A mixture of (2E)-3-(4-bromophenyl)-1-(4-fluorophenyl)prop-2-en-1-one (3.05 g, 0.01 mol) and 2,4-dinitrophenylhydrazine (1.98 g, 0.01 mol) in 50 ml of glacial acetic acid was refluxed for 6 hrs. The reaction mixture was cooled to produce red crystals (m.p. 414–416 K). X-ray quality crystals were obtained by slow evaporation of an acetic acid solution of (I) at room temperature.